U.S. patent application number 10/482546 was filed with the patent office on 2004-08-26 for multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulators/initiators.
Invention is credited to Hintermann, Tobias, Kramer, Andreas, Muhlebach, Andreas, Nesvadba, Peter, Zink, Marie-Odile.
Application Number | 20040167303 10/482546 |
Document ID | / |
Family ID | 8184009 |
Filed Date | 2004-08-26 |
United States Patent
Application |
20040167303 |
Kind Code |
A1 |
Kramer, Andreas ; et
al. |
August 26, 2004 |
Multifunctional alkoxyamines based on polyalkylpiperidines,
polyalkylpiperazinones and polyalkylmorpholinones and their use as
polymerization regulators/initiators
Abstract
The instant invention relates to multifunctional alkoxyamines
based on polyalkylpiperidines, polyalkylpiperazinones and
polyalkylmorpholinones and their use as polymerization
regulatros/initiators. Further subjects of the invention are a
polymerizable composition comprising an ethylenically unsaturated
monomer or oligomer and the alkoxyamine compound as well as a
process for polymerization and a process for preparation of the
compounds.
Inventors: |
Kramer, Andreas; (Meyriez,
CH) ; Muhlebach, Andreas; (Frick, DE) ;
Nesvadba, Peter; (Marly, CH) ; Zink, Marie-Odile;
(Mulhouse, FR) ; Hintermann, Tobias; (Basel,
CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8184009 |
Appl. No.: |
10/482546 |
Filed: |
December 30, 2003 |
PCT Filed: |
June 27, 2002 |
PCT NO: |
PCT/EP02/07131 |
Current U.S.
Class: |
526/220 ;
526/217; 526/264; 526/266; 526/303.1; 526/319; 526/335; 526/341;
526/343; 526/346; 526/348.7 |
Current CPC
Class: |
C08F 4/00 20130101; C07D
211/94 20130101 |
Class at
Publication: |
526/220 ;
526/348.7; 526/346; 526/335; 526/264; 526/266; 526/319; 526/341;
526/303.1; 526/343; 526/217 |
International
Class: |
C08F 002/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 5, 2001 |
EP |
01810664.1 |
Claims
1. A compound of formula Ia, Ib, Ic or Id 36wherein R.sub.1 and
R.sub.2 are independently of each other hydrogen,
C.sub.1-C.sub.18alkyl or phenyl; R.sub.3 is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted
by OH, or phenyl which is unsubstituted or substituted by OH,
halogen, C.sub.1-C.sub.8alkoxy or C.sub.1-C.sub.8alkyl; X is O, S,
NR.sub.4 or, if Z is --O--CH.sub.2--, X is additionally a direct
bond; R.sub.4 is hydrogen or C.sub.1-C.sub.18alkyl; Z is a direct
bond and if R.sub.1 is hydrogen and R.sub.2 phenyl, Z is
additionally --O--CH.sub.2--; Y is a radical derived from a polyol,
a polyamine, a polyaminoalcohol, a polyaminothiol, a
polyhydroxythiol, a polyaminohydroxythiol or a polythiol having 2
to 20 --OH, SH and/or --NR.sub.5H groups, wherein R.sub.5 is
hydrogen, C.sub.1-C.sub.18alkyl or phenyl; or if X is a direct bond
and Z is --O--CH.sub.2--, Y is a radical derived from a
polycarboxylic acid having 2-20 carboxylic functions A and A'
together are .dbd.O; or A' is hydrogen; and A is hydrogen,
--O--R.sub.100, wherein R.sub.100 is hydrogen,
C.sub.1-C.sub.18alkyl which is uninterrupted or interrupted by one
or more oxygen atoms, NHR.sub.100, NR.sub.100R.sub.103 or
cyanoethyl; or a group 37R.sub.101 is hydrogen, --COOH,
--COO(C.sub.1-C.sub.4alkyl), --COO-phenyl, --COObenzyl,
C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.4alkenyl, C.sub.1-C.sub.18alkyl or
C.sub.2-C.sub.4alkenyl substituted by OH, --COOH,
--COO(C.sub.1-C.sub.4)alkyl, C.sub.2-C.sub.18alkyl which may be
interrupted by one or more oxygen atom, unsubstituted cyclopentyl,
cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,
cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted
by C.sub.1-C.sub.4alkyl, --COOH or --COO--(C.sub.1-C.sub.4alkyl)
R.sub.102 is hydrogen, C.sub.1-C.sub.18alkyl or R.sub.101 and
R.sub.102 together with the nitrogen atom form a 5-membered ring
which may have an unsaturated bond or be fused to a benzene ring;
R.sub.103 is hydrogen or C.sub.1-C.sub.18alky; or A and A' together
are a group 38wherein Z.sub.1 is O, NR.sub.202 or when R.sub.201
represents alkyl or aryl Z.sub.1 is additionally a direct bond;
R.sub.202 is H, C.sub.1-C.sub.18alkyl or phenyl; R.sub.201 is H,
straight or branched C.sub.1-C.sub.18alkyl or
C.sub.3-C.sub.18alkenyl, which may be unsubstituted or substitued,
by one or more OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl- , C.sub.5C.sub.12cycloalkyl or
C.sub.5-C.sub.12cycloalkenyl; phenyl, C.sub.7-C.sub.9phenylalkyl or
naphthyl which may be unsubstituted or substituted by one or more
C.sub.1-C.sub.8alkyl, halogen, OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl; or --C(O)--C.sub.1-C.sub.18alkyl, or
an acyl moiety of a .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 9 carbon atoms or of an aromatic carboxylic acid having
7 to 15 carbon atoms; --SO.sub.3.sup.-Me.sup.+,
--PO(O.sup.-Me.sup.+).sub.2, --P(O)(OR.sub.2).sub.2,
--SO.sub.2R.sub.2, --CO--NH--R.sub.2, --CONH.sub.2, COOR.sub.2, or
Si(Me).sub.3, wherein Me.sup.+ is .dbd.H.sup.+, ammonium or an
alkali metal cation; or A is O--Y.sub.1 and A' is O--Y.sub.2
forming a ketale structure in the 4 position; wherein Y.sub.1 and
Y.sub.2 are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C7C.sub.9phenylalkyl; or Y.sub.1 and Y.sub.2 together form one of
the bivalent groups --C(R.sub.301)(R.sub.302)--CH(R.- sub.303)--,
--CH(R.sub.301)--CH.sub.2--C(R.sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2--C(R.sub.301)(R.sub.303)--,
--CH.sub.2--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 39wherein
R.sub.301 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.304; R.sub.302 and
R.sub.303 are independently hydrogen, methyl, ethyl, COOH or
COO--(C.sub.1-C.sub.12)alkyl; R.sub.304 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms.
2. A compound of formula Ia, Ib, Ic or Id according to claim 1
wherein X is O or NR.sub.4, wherein R.sub.4 is hydrogen or
C.sub.1-C.sub.8alkyl; Z is a direct bond; R.sub.1 is hydrogen or
C.sub.1-C.sub.18alkyl; and R.sub.2 is C.sub.1-C.sub.18alkyl.
3. A compound of formula Ia, Ib, Ic or Id according to claim 1
wherein A and A' together are .dbd.O; or A' is hydrogen and A is
hydrogen, OH, OR.sub.100, NHR.sub.100, NR.sub.100, R.sub.103 or a
group 40wherein R.sub.100, R.sub.101, R.sub.102 and R.sub.103
independently are hydrogen or C.sub.1-C.sub.18alkyl; or A is O--Y,
and A' is O--Y.sub.2 forming a ketale structure in the 4 position;
wherein Y.sub.1 and Y.sub.2 are independently
C.sub.1-C.sub.12alkyl, phenyl or benzyl; or Y.sub.1 and Y.sub.2
together form one of the bivalent groups --C(R.sub.301)(R.sub.302-
)--CH(R.sub.303)--,
CH(R.sub.301)--CH.sub.2--C(R.sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2--C(R.sub.301)(R.sub.303)--,
--CH.sub.2--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, or
--CH.sub.2--CH.dbd.CH--CH.sub.2--, wherein R.sub.301 is hydrogen,
C.sub.1-C.sub.12alkyl or COO--(C.sub.1-C.sub.12)alkyl; and
R.sub.302 and R.sub.303 are independently hydrogen, methyl ethyl or
COO-(C.sub.1-C.sub.12)alkyl.
4. A compound of formula Ia, Ib, Ic or Id according to claim 1
wherein Y is a radical derived from a polyol or a polyamine, having
2 to 20 --OH or --NR.sub.5H groups, wherein R.sub.5 is hydrogen,
C.sub.3-C.sub.18alkyl or phenyl.
5. A compound of formula Ia, Ib, Ic or Id according to claim 4
wherein Y is an aliphatic polyol.
6. A compound of formula Ia, Ib, Ic or Id according to claim 1
wherein n is a number from 2-10.
7. A compound of formula Ia, Ib, Ic or Id according to claim 6
wherein n is a number from 2 to 6.
8. A compound of formula Ia or Ib according to claim 1.
9. A polymerizable composition, comprising a) at least one
ethylenically unsaturated monomer or oligomer, and b) a compound of
formula Ia, Ib, Ic or Id or a mixture thereof 41wherein R.sub.1 and
R.sub.2 are independently of each other hydrogen,
C.sub.1-C.sub.18alkyl or phenyl; R.sub.3 is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted
by OH, or phenyl which is unsubstituted or substituted by OH,
halogen, C.sub.1-C.sub.8alkoxy or C.sub.1-C.sub.8alkyl; X is O, S,
NR.sub.4 or, if Z is --O--CH.sub.2--, X is additionally a direct
bond; R.sub.4 is hydrogen or C.sub.1-C.sub.18alkyl; Z is a direct
bond and if R.sub.1 is hydrogen and R.sub.2 phenyl, Z is
additionally --O--CH.sub.2--; Y is a radical derived from a polyol,
a polyamine, a polyaminoalcohol, a polyaminothiol, a
polyhydroxytiol, a polyaminohydroxythiol or a polythiol having 2 to
20 --OH, SH and/or --NR.sub.5H groups, wherein R.sub.5 is hydrogen,
C.sub.1-C.sub.18alkyl or phenyl; or if X is a direct bond and Z is
--O--CH.sub.2--, Y is a radical derived from a polycarboxylic acid
having 2-20 carboxylic functions; A and A' together are .dbd.O; or
A' is hydrogen; and A is hydrogen, --O--R.sub.100, wherein
R.sub.100 is hydrogen, C.sub.1-C.sub.18alkyl which is uninterrupted
or interrupted by one or more oxygen atoms, NHR.sub.100,
NR.sub.100R.sub.103 or cyanoethyl; or a group 42R.sub.101 is
hydrogen, --COOH, --COO(C.sub.1-C.sub.4alkyl), --COO-phenyl,
--COObenzyl, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.4alkenyl, C.sub.1-C.sub.18alkyl or
C.sub.2-C.sub.4alkenyl substituted by OH, --COOH,
--COO(C.sub.1-C.sub.4)alkyl, C.sub.2-C.sub.18alkyl which may be
interrupted by one or more oxygen atom, unsubstituted cyclopentyl,
cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,
cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted
by C.sub.1-C.sub.4alkyl, --COOH or --COO--(C.sub.1-C.sub.4alkyl)
R.sub.102 is hydrogen, C.sub.1-C.sub.18alkyl or R.sub.101 and
R.sub.102 together with the nitrogen atom form a 5-membered ring
which may have an unsaturated bond or be fused to a benzene ring;
R.sub.103 is hydrogen or C.sub.1-C.sub.18alky; or A and A' together
are a group 43wherein Z.sub.1 is O, NR.sub.202 or when R.sub.201
represents alkyl or aryl Z.sub.1 is additionally a direct bond;
R.sub.202 is H, C.sub.1-C.sub.18alkyl or phenyl; R.sub.201 is H,
straight or branched C.sub.1-C.sub.18alkyl or
C.sub.3-C.sub.18alkenyl, which may be unsubstituted or substitued,
by one or more OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl- , C.sub.5-C.sub.12cycloalkyl or
C.sub.5C.sub.12cycloalkenyl; phenyl, C.sub.7-C.sub.9phenylalkyl or
naphthyl which may be unsubstituted or substituted by one or more
C.sub.1-C.sub.8alkyl, halogen, OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl; or --C(O)--C.sub.1-C.sub.18alkyl, or
an acyl moiety of a .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 9 carbon atoms or of an aromatic carboxylic acid having
7 to 15 carbon atoms; --SO.sub.3.sup.-Me.sup.+,
--PO(O.sup.-Me.sup.+).sub.2, --P(O)(OR.sub.2).sub.2,
--SO.sub.2R.sub.2, --CO--NH--R.sub.2, --CONH.sub.2, COOR.sub.2, or
Si(Me).sub.3, wherein Me.sup.+ is .dbd.H.sub.+, ammonium or an
alkali metal cation; or A is O--Y.sub.1 and A' is O--Y.sub.2
forming a ketale structure in the 4 position; wherein Y.sub.1 and
Y.sub.2 are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7C.sub.9phenylalkyl; or Y.sub.1 and Y.sub.2 together form one
of the bivalent groups --C(R.sub.301)(R.sub.302)--CH(R.-
sub.303)--, --CH(R.sub.301)--CH.sub.2--C(R.sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2--C(R.sub.301)(R.sub.303)--,
--CH.sub.2--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, o-phenylene,
1,2-cyclohexyliden, --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 44wherein
R.sub.301 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.304; R.sub.302 and
R.sub.303 are independently hydrogen, methyl, ethyl, COOH or
COO-(C.sub.1-C.sub.12)alkyl; R.sub.304 is hydrogen,
C.sub.1-C.sub.12alkyl, benzyl, or a monovalent acyl residue derived
from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid
having up to 18 carbon atoms.
10. A composition according to claim 9, wherein the ethylenically
unsaturated monomer or oligomer is selected from the group
consisting of ethylene, propylene, n-butylene, n-butylene, styrene,
substituted styrene, conjugated dienes, acrolein, vinyl acetate,
vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic
acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters,
(meth)acrylonitriles, (alkyl)acrylamides, vinyl halides or
vinylidene halides.
11. A composition according to claim 9, wherein the ethylenically
unsaturated monomers are ethylene, propylene, n-butylene,
i-butylene, isoprene, 1,3-butadiene,
.alpha.-C.sub.5-C.sub.18alkene, styrene, .alpha.-methyl styrene,
p-methyl styrene or a compound of formula
CH.sub.2.dbd.C(R.sub.a)--(C.dbd.Z)--R.sub.b, wherein R.sub.a is
hydrogen or C.sub.1-C.sub.4alkyl, R.sub.b is NH.sub.2,
O.sup.-(Me.sup.+), glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy,
C.sub.2-C.sub.100alkoxy interrupted by at least one N and/or O
atom, or hydroxy-substituted C.sub.1-C.sub.18alkoxy, unsubstituted
Cl-C.sub.18alkylamino, di(C.sub.1-C.sub.48alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.18alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.18alky- l)amino,
--O--CH.sub.2CH.sub.2N(CH.sub.3).sub.2 or --O--CH.sub.2--CH.sub.2-
--N.sup.+H(CH.sub.3).sub.2 An.sup.-; An.sup.- is a anion of a
monovalent organic or inorganic acid; Me is a monovalent metal atom
or the ammonium ion. Z is oxygen or sulfur.
12. A composition according to claim 9, wherein the compound of
formula Ia, Ib, Ic or Id is present in an amount of from 0.01 mol-%
to 20 mol-%,
13. A process for preparing an oligomer, a cooligomer, a polymer or
a copolymer (block or random) by free radical polymerization of at
least one ethylenically unsaturated monomer or oligomer, which
comprises (co)polymerizing the monomer or monomers/oligomers in the
presence of an initiator compound of formula Ia, Ib, Ic or Id under
reaction conditions capable of effecting scission of the O--C bond
to form two free radicals, the radical 45being capable of
initiating polymerization.
14. A process according to claim 13, wherein'the scission of the
O--C bond is effected by heating and takes place at a temperature
of between 50.degree. C. and 160.degree. C.
15. A process for the preparation of a compound of Formula Ia, Ib,
Ic or Id which process comprises the steps of a) reacting a
compound of formula IIa, IIb, IIc or IId 46with a compound of
formula III 47having a radically transferable group Hal, with a
transition metal or transition metal compound in the absence of
oxygen; wherein the substituents are as defined in claim 1; b)
subjecting the reaction mixture to a reduction step; c) washing the
resulting mixture with an aqueous acid solution and isolating the
product.
16. Use of a compound of formula Ia, Ib, Ic or Id for the
controlled radical (co)polymerization of ethylenically unsaturated
monomers.
Description
[0001] The instant invention relates to multifunctional
alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones
and polyalkylmorpholinones and their use as polymerization
regulators/initiators. Further subjects of the invention are a
polymerizable composition comprising an ethylenically unsaturated
monomer or oligomer and the alkoxyamine compound as well as a
process for polymerization and a process for preparation of the
compounds.
[0002] The initiators/regulators, the polymerization processes and
resin products of the present invention are useful in many
applications, including a variety of specialty applications, such
as for the preparation of block copolymers which are useful as
compatibilizing agents for polymer blends, or dispersing agents for
coating systems or for the preparation of narrow molecular weight
resins or oligomers for use in coating technologies and
thermoplastic films or as toner resins and liquid immersion
development ink resins or ink additives used for
electrophotographic imaging processes.
[0003] The concept of having multifunctional alkoxyamines as
initiators/regulators for radical polymerization is known. WO
00/71501 for example discloses multifunctional open chain
alkoxyamines having a phosphor atom attached to the carbon atom in
.alpha.-position to the nitrogen atom. The compounds are useful
initiators/regulators, however, they are thermally not very stable
and can only be used at a polymerization temperature of around
120.degree. C. Limited storage stability is a further drawback of
these compounds.
[0004] U.S. Pat. No. 5,627,248 and U.S. Pat. No. 5,677,388 disclose
difunctional alkoxyamines on the basis of tetramethylpiperidine.
These compounds are not very reactive and only the polymerization
of styrene proceeds with reasonable efficiency at high
temperatures. Conversion and polymerization rate of acrylates is
very low.
[0005] WO 00/18807 discloses polymeric macroinitiators which have
been prepared by ATRP polymerization wherein the halogen atoms have
been replaced by nitroxylether end groups.
[0006] WO 01/02345 discloses also multifunctional alkoxyamines.
These compounds are all characterized by having a phenyl group
attached to the carbon atom in .alpha.-position to the oxygen atom
of the alkoxyamine group. This aromatic group can have drawbacks in
the end use of the polymers. Typically photo stability decreases,
when aromatic moieties are present. This leads in many cases to
discoloration which is undesirable for many end uses.
[0007] Surprisingly, it has now been found that the present
compounds are very suitable to prepare (co)polymers particularly
block, star, comb (co)polymers and the like, without having the
drawbacks of the prior art compounds.
[0008] By their multiple alkoxyamine functionality they provide an
ideal tool for tailor made polymerization processes. The degree of
branches can be chosen by selecting two, three, four or even more
alkoxyamine functionalities.
[0009] Furthermore with the present invention there are provided
initiators/regulators which allow very efficiently to bring into
the macromer functional end-groups which come from the initiating
radical. The compounds of the present invention thus allow to
produce macromers or polymers with a wide variety of functional
groups, which was not easily possible until now.
[0010] The functionalized macromers or polymers may then be further
reacted with suitable modifying compounds to further adjust the
polymer's properties.
[0011] Polymerization of the monomers results in a polymer or
copolymer of narrow polydispersity, higher molecular weight and a
high monomer to polymer conversion even at relatively low
temperatures and at short reaction times, making the polymerization
process particularly suitable for industrial applications. The
resulting (co)polymers are of high purity and in many cases
colorless, therefore not requiring any further purification. The
polymers prepared with the instant compounds show high photo and
thermal stability and exhibit only a minor discoloration upon
exposure to UV light and heat due to the higher alkoxyamine
content.
[0012] One subject of the invention is a compound of formula Ia,
Ib, Ic or Id 1
[0013] wherein
[0014] R.sub.1 and R.sub.2 are independently of each other
hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0015] R.sub.3 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18alkyl which is substituted by OH, or phenyl which
is unsubstituted or substituted by OH, halogen,
C.sub.1-C.sub.8alkoxy or C.sub.1-C.sub.8alkyl;
[0016] X is O, S, NR.sub.4 or, if Z is --O--CH.sub.2--, X is
additionally a direct bond;
[0017] R.sub.4 is hydrogen or C.sub.1-C.sub.18alkyl;
[0018] Z is a direct bond and if R.sub.1 is hydrogen and R.sub.2
phenyl, Z is additionally --O--CH.sub.2--;
[0019] Y is a radical derived from a polyol, a polyamine, a
polyaminoalcohol, a polyaminothiol, a polyhydroxythiol, a
polyaminohydroxythiol or a polythiol having 2 to 20 --OH, SH and/or
--NR.sub.5H groups, wherein R.sub.5 is hydrogen,
C.sub.1-C.sub.18alkyl or phenyl;
[0020] or if X is a direct bond and Z is --O--CH.sub.2--, Y is a
radical derived from a polycarboxylic acid having 2-20 carboxylic
functions;
[0021] A and A' together are .dbd.O; or
[0022] A' is hydrogen; and
[0023] A is hydrogen, --O--R.sub.100, wherein R.sub.100 is
hydrogen, C.sub.1-C.sub.18alkyl which is uninterrupted or
interrupted by one or more oxygen atoms, NHR.sub.100,
NR.sub.100R.sub.103 or cyanoethyl;
[0024] or a group 2
[0025] R.sub.101 is hydrogen, --COOH, --COO(C.sub.1-C.sub.4alkyl),
--COO-phenyl, --COObenzyl, C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.4alkenyl,
C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.4alkenyl substituted by OH,
--COOH, --COO(C.sub.1-C.sub.4)alkyl, C.sub.2-C.sub.18alkyl which
may be interrupted by one or more oxygen atom, unsubstituted
cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl; or
cyclopentyl, cyclohexyl, cylohexenyl, phenyl or naphthyl which are
substituted by C.sub.1-C.sub.4alkyl, --COOH or
--COO--(C.sub.1-C.sub.4alkyl)
[0026] R.sub.102 is hydrogen, C.sub.1-C.sub.18alkyl or R.sub.101
and R.sub.102 together with the nitrogen atom form a 5-membered
ring which may have an unsaturated bond or be fused to a benzene
ring;
[0027] R.sub.103 is hydrogen or C.sub.1-C.sub.18alky; or
[0028] A and A' together are a group 3
[0029] wherein
[0030] Z.sub.1 is O.sub.1 NR.sub.202 or when R.sub.20, represents
alkyl or aryl Z.sub.1 is additionally a direct bond;
[0031] R.sub.202 is H, C.sub.1-C.sub.18alkyl or phenyl;
[0032] R.sub.201 is H, straight or branched C.sub.1-C.sub.18alkyl
or C.sub.3-C.sub.18alkenyl, which may be unsubstituted or
substitued, by one or more OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl- , C.sub.5-C.sub.12cycloalkyl or
C.sub.5C.sub.12cycloalkenyl;
[0033] phenyl, C.sub.7-C.sub.9phenylalkyl or naphthyl which may be
unsubstituted or substituted by one or more C.sub.1-C.sub.8alkyl,
halogen, OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbony- l; or
[0034] --C(O)-C.sub.1-C.sub.18alkyl, or an acyl moiety of a
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 9 carbon
atoms or of an aromatic carboxylic acid having 7 to 15 carbon
atoms;
[0035] SO.sub.3.sup.-Me.sup.+, --PO(O.sup.-Me.sup.+).sub.2,
--P(O)(OR.sub.2).sub.2, --SO.sub.2R.sub.2, --CO--NH--R.sub.2,
--CONH.sub.2, COOR.sub.2, or Si(Me).sub.3, wherein Me.sup.+ is
.dbd.H.sup.+, ammonium or an alkali metal cation; or
[0036] A is O--Y.sub.1 and A' is O--Y.sub.2 forming a ketale
structure in the 4 position; wherein
[0037] Y.sub.1 and Y.sub.2 are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7-C.sub.9phenylalkyl; or
[0038] Y.sub.1 and Y.sub.2 together form one of the bivalent groups
--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--,
--CH(R.sub.301)--CH.sub.2--C(- R.sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2--C(R.sub.301)(R.sub.303- )--,
--CH.sub.2--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, o-phenylene,
1,2-cyclohexyliden,
[0039] --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 4
[0040] wherein
[0041] R.sub.301 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO--(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.304;
[0042] R.sub.302 and R.sub.303 are independently hydrogen, methyl,
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0043] R.sub.304 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms.
[0044] Halogen is F, Cl, Br, I, preferably Cl or Br.
[0045] C.sub.1-C.sub.18alkyl can be linear or branched. Examples
are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl,
t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,
t-octyl, nonyl, decyl, undecyl or dodecyl.
[0046] C.sub.2-C.sub.18alkyl interrupted by at least one O atom is
for example --CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.3, --CH.sub.2
CH.sub.2--O--CH.sub.3 or
--CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2CH.sub.2O-
--CH.sub.2--CH.sub.3. It is preferably derived from polyethlene
glycol. A general description is
--((CH.sub.2).sub.a--O).sub.b--H/CH.sub.3, wherein a is a number
from 1 to 6 and b is a number from 2 to 10.
[0047] Further examples of C.sub.2-C.sub.18alkyl interrupted by
--O-- are for example 3-oxapentane, 4 oxaheptane, 3,6-dioxaoctane,
4,7-dioxadecane, 4,9-dioxadodecane, 3,6,9-trioxaundecane and
4,7,10-trioxatridecane.
[0048] Alkyl substituted by a group --COOH is for example
CH.sub.2--COOH, CH.sub.2--CH.sub.2COOH, (CH.sub.2).sub.3--COOH or
CH.sub.2--CHCOOH--CH.su- b.2--CH.sub.3
[0049] Hydroxyl- or alkoxycarbonyl substituted
C.sub.1-C.sub.18alkyl can be, for example, 2-hydroxyethyl,
2-hydroxypropyl, methoxycarbonylmethyl or 2-ethoxycarbonylethyl,
2-hydroxyethyl is preferred.
[0050] Alkenyl having from 3 to 18 carbon atoms is a branched or
unbranched radical, for example propenyl, 2-butenyl, 3-butenyl,
isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl,
n-2-dodecenyl, isododecenyl.
[0051] Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy,
butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or
octoxy.
[0052] Aryl is phenyl or naphthyl.
[0053] C.sub.7-C.sub.9phenylalkyl is for example benzyl,
.alpha.-methylbenzyl, .alpha.,.alpha.-dimethylbenzyl or
2-phenylethyl, benzyl is preferred.
[0054] C.sub.5-C.sub.12cycloalkyl is for example cyclopentyl,
cyclohexyl, cycloheptyl, methylcyclopentyl or cyclooctyl.
[0055] C.sub.5-C.sub.12cycloalkenyl is for example 3-cyclopentenyl,
3-cyclohexenyl or 3-cycloheptenyl.
[0056] If R.sub.1 is a monovalent radical of a .alpha.,
.beta.-unsaturated or aromatic carboxylic acid, it is, for example,
an acryloyl, methacryloyl, benzoyl or
.beta.-(3,5di-tert-butyl-4-hydroxyphenyl)propion- yl radical.
[0057] A monovalent radical of an aliphatic carboxylic acid is for
example acetyl, propionyl, butyryl, caproyl, stearoyl or oleyl.
[0058] Preferred is a compound of formula Ia, Ib, Ic or Id
wherein
[0059] X is O or NR.sub.4, wherein R.sub.4 is hydrogen or
C.sub.1-C.sub.8alkyl;
[0060] Z is a direct bond;
[0061] R.sub.1 is hydrogen or C.sub.1-C.sub.18alkyl; and
[0062] R.sub.2 is C.sub.1-C.sub.18alkyl and the other substituents
are as defined above.
[0063] More preferred is a compound of formula Ia, Ib, Ic or Id
wherein
[0064] A and A' together are .dbd.O; or
[0065] A' is hydrogen and
[0066] A is hydrogen, OH, OR.sub.100,
NHR.sub.100NR.sub.100R.sub.103 or a group 5
[0067] wherein R.sub.100, R.sub.101, R.sub.102 and R.sub.103
independently are hydrogen or C.sub.1-C.sub.18alkyl; or
[0068] A is O--Y.sub.1 and A' is O--Y.sub.2 forming a ketale
structure in the 4 position; wherein
[0069] Y.sub.1 and Y.sub.2 are independently C.sub.1-C.sub.12alkyl,
phenyl or benzyl; or
[0070] Y.sub.1 and Y.sub.2 together form one of the bivalent groups
--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--,
CH(R.sub.301)--CH.sub.2--C(R.- sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2--C(R.sub.301)(R.sub.303)-- -,
--CH.sub.2--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, or
--CH.sub.2--CH.dbd.CH--CH.sub.2--, wherein
[0071] R.sub.301 is hydrogen, C.sub.1-C.sub.12alkyl or
COO--(C.sub.1-C.sub.12)alkyl; and
[0072] R.sub.302 and R.sub.303 are independently hydrogen, methyl
ethyl or COO--(C.sub.1-C.sub.12)alkyl.
[0073] Y is an organic radical derived from a polyfunctional
alcohol, polyfunctional aminoalcohol, polyfunctional amine,
polyfunctional mercaptane, polyfunctional phenol or polyfunctional
thiophenol.
[0074] The polyfunctional alcohol can be an aliphatic
polyfunctional alcohol, a cycloaliphatic polyol or an aromatic
polyol.
[0075] The aliphatic polyfunctional alcohol can contain 2 to 20
carbon atoms, the cycloaliphatic polyols 5 to 12 carbon atoms and
the aromatic polyols 6 to 18 carbon atoms.
[0076] Polyoxyalkylene glycols having a molecular weight from 150
to 40000 can also be used.
[0077] Aromatic polyols are those, wherein at least two hydroxyl
groups are bound to one or to different aromatic hydrocarboxylic
radicals.
[0078] Suitable aliphatic polyols are for example diols which are
linear or branched aliphatic glycols, in particular those
containing 2 to 12, preferably 2 to 6, carbon atoms in the
molecule, for example: ethylene glycol, 1,2- and 1,3-propylene
glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, pentyl glycol,
neopentyl glycol, 1,6-hexanediol, 1,12-dodecanediol. A suitable
cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane.
Other suitable aliphatic diols are, for example,
1,4-bis(hydroxymethyl)cyclohexane, aromatic-aliphatic diols, such
as p-xylylene glycol or 2,5-dichloro-p-xylylene glycol,
2,2-(.beta.-hydroxyethoxyphenyl)propane and polyoxyalkylene
glycols, such as diethylene glycol, triethylene glycol,
polyethylene glycol or polypropylene glycol. The alkylenediols are
preferably linear and preferably contain 2 to 4 carbon atoms.
[0079] Other suitable diols are the .beta.-hydroxyalkylated, in
particular .beta.-hydroxyethylated bisphenols, such as
2,2-bis[4'-(.beta.-hydroxyeth- oxy)phenyl]propane.
[0080] Another group of suitable aliphatic diols are the
heterocyclic diols described in the German published patent
specifications 1812003, 2342432, 2342372 and 2453326. Examples are:
N,N'-bis(.beta.-hydroxyethyl)- -5,5-dimethylhydantoin,
N,N'-bis(.beta.-hydroxypropyl)-5,5-dimethylhydanto- in,
methylenebis-[N-(.beta.-hydroxyethyl)-5-methyl-5-ethylhydantoin],
methylenebis-[N-(.beta.-hydroxyethyl)-5,5-dimethylhydantoin],
N,N'-bis(.beta.-hydroxyethyl)benzimidazolone,
N,N'-bis(.beta.-hydroxyethy- l)-(tetrachloro)benzimidazolone or
N,N'-bis(.beta.-hydroxyethyl)-(tetrabro- mo)benzimidazolone.
[0081] Suitable aromatic diols are mononuclear diphenols and, in
particular, dinuclear diphenols carrying a hydroxyl group at each
aromatic nucleus. The term aromatic will be taken to mean
preferably hydrocarbonaromatic radicals such as phenylene or
naphthylene. Besides e.g. hydroquinone, resorcinol or 1,5-, 2,6-
and 2,7-dihydroxynaphthalene, 9,10-dihydroxyanthracene,
4,4'-dihydroxybiphenyl, bisphenols merit particular mention.
[0082] Examples of bisphenols are: bis(p-hydroxyphenyl) ether or
bis(p-hydroxyphenyl) thioether, bis(p-hydroxyphenyl)sulfone,
bis(p-hydroxyphenyl)methane, bis(4-hydroxyphenyl)-2,2'-biphenyl,
phenylhydroquinone, 1,2-bis(p-hydroxyphenyl)ethane,
1-phenyl-bis(p-hydroxyphenyl)methane,
diphenyl-bis(p-hydroxyphenyl)methan- e,
diphenyl-bis(p-hydroxyphenyl)ethane,
bis(3,5-dimethylhydroxyphenyl)sulf- one, bis(3,5-dimethyl
hydroxyphenyl)-p-diisopropylbenzene,
bis(3,5-dimethylhydroxyphenyl)-m-diisopropylbenzene,
2,2-bis(3',5'-dimethyl-4'-hydroxyphenyl)propane, 1,1- or
2,2-bis(p-hydroxyphenyl)butane,
2,2-bis(p-hydroxyphenyl)hexafluoropropane- , 1,1-dichloro- or
1,1,1-trichloro-2,2-bis(phydroxyphenyl)ethane,
1,1-bis(p-hydroxyphenyl)cyclopentane and, in particular,
2,2-bis(p-hydroxyphenyl)propane (bisphenol-A) and
1,1-bis(p-hydroxyphenyl- )cyclohexane (bisphenol-C).
[0083] A suitable triol is for example 6
[0084] R.dbd.CH.sub.2--CH.sub.2--OH.
[0085] Other suitable aliphatic triols are for example glycerin or
trimethylolpropane.
[0086] Examples for a tetrafunctional alcohol are erythritol,
threitol or pentaerythritol.
[0087] Higher alcohols are for example pentahydroles, for example
xylitol or arabitol and hexahydrols, for example sorbitol,
mannitol, dulcitol, talitol, iditol, inositol.
[0088] In principal all hydroxylated aliphatic hydrocarbon
compounds are suitable as multifunctional alcohols.
[0089] The polyaminoalcohols or polyamines can be deduced from the
above mentioned polyalcohols by replacing one or more hydroxyl
groups by amino groups.
[0090] Primary amino groups are preferred, which may be attached to
aromatic rings or alkyl groups as mentioned above for the
corresponding alcohols.
[0091] Suitable mercaptanes or thiophenols are those which are
derived by substituting the oxygen atom by a sulfur atom in the
above mentioned examples.
[0092] If X is a direct bond and Z is --O--CH.sub.2--, then Y is a
radical derived from a polycarboxylic acid having 2-20 carboxylic
functions.
[0093] Suitable polycarboxylic acids are for example dicarboxylic
acids like oxalic acid, malonic acid, succinic acid, fumaric acid,
glutaric acid, adipic acid, 1,12-dodecandioic acid, phthalic-,
isophthalic- or terephthalic acid, isomeric naphthalene
dicarboxylic acids, tricarboxylic acids like citric acid,
nitrilotriacetic acid or 1,2,4-benzentricarboxyli- c acid,
tetracarboxylic acids like ethylenediamine tetraacetic acid or
pyromellitic acid, pentacarboxylic acids like for example
diethylenetriaminepentaacetic acid, hexacarboxylic acids like for
example mellitic acid or triethylenetetraminehexaacetic acid.
[0094] Preferably Y is a radical derived from a polyol or
polyamine, having 2 to 20 --OH or --NR.sub.5H groups, wherein R; is
hydrogen, C.sub.1-C.sub.18alkyl or phenyl.
[0095] More preferably Y is an aliphatic polyol. Examples have been
already mentioned.
[0096] Preferably n is a number from 2-20, more preferably from
2-10 and most preferably from 2-6.
[0097] Most preferred is a compound of formula Ia or Ib, to which
the preferences given above may also apply.
[0098] Particularly suitable compounds are 7
[0099] compound 101 of Table 1, 8
[0100] compound 107 of Table 1, 9
[0101] compound 109 of Table 1 and 10
[0102] compound 110 of Table 1.
[0103] A further subject of the invention is a polymerizable
composition, comprising
[0104] a) at least one ethylenically unsaturated monomer or
oligomer, and
[0105] b) a compound of formula Ia, Ib, Ic or Id or a mixture
thereof 11
[0106] wherein
[0107] R.sub.1 and R.sub.2 are independently of each other
hydrogen, C.sub.1-C.sub.18alkyl or phenyl;
[0108] R.sub.3 is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.1-C.sub.18alkyl which is substituted by OH, or phenyl which
is unsubstituted or substituted by OH, halogen,
C.sub.1-C.sub.8alkoxy or C.sub.1-C.sub.8alkyl;
[0109] X is O, S, NR.sub.4 or, if Z is --O--CH.sub.2, X is
additionally a direct bond;
[0110] R.sub.4 is hydrogen or C.sub.1-C.sub.18alkyl;
[0111] Z is a direct bond and if R.sub.1 is hydrogen and R.sub.2
phenyl, Z is additionally --O--CH.sub.2--;
[0112] Y is a radical derived from a polyol, a polyamine, a
polyaminoalcohol, a polyaminothiol, a polyhydroxythiol, a
polyaminohydroxythiol or a polythiol having 2 to 20 --OH, SH and/or
--NR.sub.5H groups, wherein R.sub.5 is hydrogen,
C.sub.1-C.sub.18alkyl or phenyl;
[0113] or if X is a direct bond and Z is --O--CH.sub.2--, Y is a
radical derived from a polycarboxylic acid having 2-20 carboxylic
functions;
[0114] A and A' together are .dbd.O; or
[0115] A' is hydrogen; and
[0116] A is hydrogen, --O--R.sub.100, wherein R.sub.100 is
hydrogen, C.sub.1-C.sub.18alkyl which is uninterrupted or
interrupted by one or more oxygen atoms, NHR.sub.100,
NR.sub.100R.sub.103 or cyanoethyl;
[0117] or a group 12
[0118] R.sub.101 is hydrogen, --COOH, --COO(C.sub.1-C.sub.4alkyl),
--COO-phenyl, --COObenzyl, C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.4alkenyl,
C.sub.1-C.sub.18alkyl or C.sub.2-C.sub.4alkenyl substituted by OH,
--COOH, --COO(C.sub.1-C.sub.4)alkyl, C.sub.2-C.sub.18alkyl which
may be interrupted by one or more oxygen atom, unsubstituted
cyclopentyl, cyclohexyl, cyclohexenyl, phenyl or naphthyl; or
cyclopentyl, cyclohexyl, cylohexenyl, phenyl or naphthyl which are
substituted by C.sub.1-C.sub.4alkyl, --COOH or
--COO--(C.sub.1-C.sub.4alkyl)
[0119] R.sub.102 is hydrogen, C.sub.1-C.sub.18alkyl or R.sub.101,
and R.sub.102 together with the nitrogen atom form a 5-membered
ring which may have an unsaturated bond or be fused to a benzene
ring;
[0120] R.sub.103 is hydrogen or C.sub.1-C.sub.18alkyl; or
[0121] A and A' together are a group 13
[0122] wherein
[0123] Z.sub.1 is O, NR.sub.202 or when R.sub.201 represents alkyl
or aryl Z.sub.1 is additionally a direct bond;
[0124] R.sub.202 is H, C.sub.1-C.sub.18alkyl or phenyl;
[0125] R.sub.201 is H, straight or branched C.sub.1-C.sub.18alkyl
or C.sub.3-C.sub.18alkenyl, which may be unsubstituted or
substitued, by one or more OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbonyl- , C.sub.5-C.sub.12cycloalkyl or
C.sub.5-C.sub.12cycloalkenyl;
[0126] phenyl, C.sub.7C.sub.9phenylalkyl or naphthyl which may be
unsubstituted or substituted by one or more C.sub.1-C.sub.8alkyl,
halogen, OH, C.sub.1-C.sub.8alkoxy, carboxy,
C.sub.1-C.sub.8alkoxycarbony- l; or
[0127] --C(O)-C.sub.1-C.sub.18alkyl, or an acyl moiety of a
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 9 carbon
atoms or of an aromatic carboxylic acid having 7 to 15 carbon
atoms;
[0128] --SO.sub.3.sup.-Me.sup.+, --PO(O'Me.sup.+).sub.2,
--P(O)(OR.sub.2).sub.2, --SO.sub.2R.sub.2, --CO--NH--R.sub.2,
--CONH.sub.2, COOR.sub.2, or Si(Me).sub.3, wherein Me.sup.+ is
.dbd.H.sup.+, ammonium or an alkali metal cation; or
[0129] A is O--Y, and A' is O--Y.sub.2 forming a ketale structure
in the 4 position; wherein
[0130] Y.sub.1 and Y.sub.2 are independently C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.3-C.sub.12alkinyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl, naphthyl,
C.sub.7C.sub.9phenylalkyl; or
[0131] Y.sub.1 and Y.sub.2 together form one of the bivalent groups
--C(R.sub.301)(R.sub.302)--CH(R.sub.303)--,
--CH(R.sub.301)--CH.sub.2--C(- R.sub.302)(R.sub.303)--,
--CH(R.sub.302)--CH.sub.2C(R.sub.301)(R.sub.303)-- -,
--CH.sub.2C(R.sub.301)(R.sub.302)--CH(R.sub.303)--, o-phenylene,
1,2-cyclohexyliden,
[0132] --CH.sub.2--CH.dbd.CH--CH.sub.2-- or 14
[0133] wherein
[0134] R.sub.301 is hydrogen, C.sub.1-C.sub.12alkyl, COOH,
COO-(C.sub.1-C.sub.12)alkyl or CH.sub.2OR.sub.304;
[0135] R.sub.302 and R.sub.303 are independently hydrogen, methyl,
ethyl, COOH or COO--(C.sub.1-C.sub.12)alkyl;
[0136] R.sub.304 is hydrogen, C.sub.1-C.sub.12alkyl, benzyl, or a
monovalent acyl residue derived from an aliphatic, cycloaliphatic
or aromatic monocarboxylic acid having up to 18 carbon atoms.
[0137] Definitions and preferences for the individual substituents
have been mentioned above.
[0138] Preferably the initiator/regulator compound of formula (Ia),
(Ib), (Ic) or (Id) is present in an amount of from 0.01 mol-% to 20
mol-% more preferably in an amount of from 0.01 mol-% to 10 mol-%
and most preferred in an amount of from 0.05 mol-% to 10 mol-%
based on the monomer or monomer mixture.
[0139] It is also possible to use a mixture of different
initiators/regulators.
[0140] When monomer mixtures are used mol-% is calculated on the
average molecular weight of the mixture.
[0141] Preferably the ethylenically unsaturated monomer or oligomer
is selected from the group consisting of ethylene, propylene,
n-butylene, n-butylene, styrene, substituted styrene, conjugated
dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole,
maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic
acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,
(alkyl)acrylamides, vinyl halides or vinylidene halides.
[0142] Particularly the ethylenically unsaturated monomers are
ethylene, propylene, n-butylene, i-butylene, isoprene,
1,3-butadiene, .alpha.-C.sub.5-C.sub.18alkene, styrene,
.alpha.-methyl styrene, p-methyl styrene or a compound of formula
CH.sub.2.dbd.C(R.sub.a)--(C.dbd.Z)--R.su- b.b, wherein R.sub.a is
hydrogen or C.sub.1-C.sub.4alkyl, R.sub.b is NH.sub.2,
O.sup.-(Me.sup.+), glycidyl, unsubstituted C.sub.1-C.sub.18alkoxy,
C.sub.2-C.sub.100alkoxy interrupted by at least one N and/or O
atom, or hydroxy-substituted C.sub.1-C.sub.18alkoxy, unsubstituted
C.sub.1-C.sub.18alkylamino, di(C.sub.1-C.sub.18alkyl)amino,
hydroxy-substituted C.sub.1-C.sub.18alkylamino or
hydroxy-substituted di(C.sub.1-C.sub.18alkyl)amino,
--O--CH.sub.2--CH.sub.2--N(CH.sub.3).sub.- 2 or
--O--CH.sub.2--CH.sub.2--N.sup.+H(CH.sub.3).sub.2 An.sup.-;
[0143] An.sup.-' is a anion of a monovalent organic or inorganic
acid;
[0144] Me is a monovalent metal atom or the ammonium ion.
[0145] Z is oxygen or sulfur.
[0146] Examples for R.sub.a as C.sub.2-C.sub.100alkoxy interrupted
by at least one O atom are of formula 15
[0147] wherein R.sub.c is C.sub.1-C.sub.25alkyl, phenyl or phenyl
substituted by C.sub.1-C.sub.18alkyl, R.sub.d is hydrogen or methyl
and v is a number from 1 to 50. These monomers are for example
derived from non ionic surfactants by acrylation of the
corresponding alkoxylated alcohols or phenols. The repeating units
may be derived from ethylene oxide, propylene oxide or mixtures of
both.
[0148] Further examples of suitable acrylate or methacrylate
monomers are given below. 16
[0149] wherein An.sup.- and R.sub.a have the meaning as defined
above and R.sub.e is methyl or benzyl. An.sup.- is preferably
Cl.sup.-, Br.sup.- or .sup.-O.sub.3S--CH.sub.3.
[0150] Further acrylate monomers are 17
[0151] Examples for suitable monomers other than acrylates are
18
[0152] Preferably R.sub.a is hydrogen or methyl, R.sub.b is
NH.sub.2, gycidyl, unsubstituted or with hydroxy substituted
C.sub.1-C.sub.4alkoxy, unsubstituted C.sub.1-C.sub.4alkylamino,
di(C.sub.1-C.sub.4alkyl)amino, hydroxy-substituted
C.sub.1-C.sub.4alkylamino or hydroxy-substituted
di(C.sub.1-C.sub.4alkyl)amino; and
[0153] Z is oxygen.
[0154] Particularly preferred ethylenically unsaturated monomers
are styrene, methylacrylate, ethylacrylate, butylacrylate,
isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate,
hydroxypropylacrylate, dimethylaminoethylacrylate,
glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate,
butyl(meth)acrylate, hydroxyethyl(meth)acrylate,
hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,
glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide
or dimethylaminopropyl-methacrylamide.
[0155] A further subject of the invention is a process for
preparing an oligomer, a cooligomer, a polymer or a copolymer
(block or random) by free radical polymerization of at least one
ethylenically unsaturated monomer or oligomer, which comprises
(co)polymerizing the monomer or monomers/oligomers in the presence
of an initiator compound of formula (Ia), (Ib), (Ic) or (Id) under
reaction conditions capable of effecting scission of the O--C bond
to
[0156] form two free radicals, the radical 19
[0157] being capable of initiating polymerization.
[0158] Preferred is a process wherein the scission of the O--C bond
is effected by ultrasonic treatment, heating or exposure to
electromagnetic radiation, ranging from .gamma. to microwaves.
[0159] More preferably the scission of the O--C bond is effected by
heating and takes place at a temperature of between 50.degree. C.
and 160.degree. C.
[0160] The process may be carried out in the presence of an organic
solvent or in the presence of water or in mixtures of organic
solvents and water. Additional cosolvents or surfactants, such as
glycols or ammonium salts of fatty acids, may be present. Other
suitable cosolvents are described hereinafter.
[0161] Preferred processes use as little solvents as possible. In
the reaction mixture it is preferred to use more than 30% by weight
of monomer and initiator, particularly preferably more than 50% and
most preferrably more than 80%.
[0162] If organic solvents are used, suitable solvents or mixtures
of solvents are typically pure alkanes (hexane, heptane, octane,
isooctane), hydrocarbons (benzene, toluene, xylene), halogenated
hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene
glycol, ethylene glycol monomethyl ether), esters (ethyl acetate,
propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl
ether, ethylene glycol dimethyl ether), or mixtures thereof.
[0163] The aqueous polymerization reactions can be supplemented
with a water-miscible or hydrophilic cosolvent to help ensure that
the reaction mixture remains a homogeneous single phase throughout
the monomer conversion. Any water-soluble or water-miscible
cosolvent may be used, as long as the aqueous solvent medium is
effective in providing a solvent system which prevents
precipitation or phase separation of the reactants or polymer
products until after all polymerization reactions have been
completed. Exemplary cosolvents useful in the present invention may
be selected from the group consisting of aliphatic alcohols,
glycols, ethers, glycol ethers, pyrrolidines, N-alkyl
pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,
polypropylene glycols, amides, carboxylic acids and salts thereof,
esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,
hydroxyether derivatives such as butyl carbitol or cellosolve,
amino alcohols, ketones, and the like, as well as derivatives
thereof and mixtures thereof. Specific examples include methanol,
ethanol, propanol, dioxane, ethylene glycol, propylene glycol,
diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran,
and other water-soluble or water-miscible materials, and mixtures
thereof. When mixtures of water and water-soluble or water-miscible
organic liquids are selected as the aqueous reaction media, the
water to cosolvent weight ratio is typically in the range of about
100:0 to about 10:90.
[0164] The process is particularly useful for the preparation of
block copolymers.
[0165] Block copolymers are, for example, block copolymers of
polystyrene and polyacrylate (e.g., poly(styrene-co-acrylate) or
poly(styrene-co-acrylate-co-styrene). They are usefull as adhesives
or as compatibilizers for polymer blends or as polymer toughening
agents. Poly(methylmethacrylate-co-acrylate) diblock copolymers or
poly(methylacrylate-co-acrylate-co-methacrylate) triblock
copolymers) are useful as dispersing agents for coating systeme, as
coating additives (e.g. rheological agents, compatibilizers,
reactive diluents) or as resin component in coatings (e.g. high
solid paints) Block copolymers of styrene, (meth)acrylates and/or
acrylontrile are useful for plastics, elastomers and adhesives.
[0166] Furthermore, block copolymers of this invention, wherein the
blocks alternate between polar monomers and non-polar monomers, are
useful in many applications as amphiphilic surfactants or
dispersants for preparing highly uniform polymer blends.
[0167] The (co)polymers of the present invention may have a number
average molecular weight from 1000 to 400000 g/mol, preferably from
2000 to 250000 g/mol and, more preferably, from 2000 to 200000
g/mol. When produced in bulk, the number average molecular weight
may be up to 500000 (with the same minimum weights as mentioned
above). The number average molecular weight may be determined by
size exclusion chromatography (SEC), gel permeation chromatography
(GPC), matrix assisted laser desorption/ionization mass
spectrometry (MALDI-MS) or, if the initiator carries a group which
can be easily distinguished from the monomer(s), by NMR
spectroscopy or other conventional methods.
[0168] The polymers or copolymers of the present invention have
preferably a polydispersity of from 1.0 to 2, more preferably of
from 1.1 to 1.9 and most preferably from 1.1 to 1.8.
[0169] Thus, the present invention also encompasses in the
synthesis novel block, multi-block, star, gradient, random,
hyperbranched and dendritic copolymers, as well as graft or
copolymers.
[0170] The polymers prepared by the present invention are useful
for following applications:
[0171] adhesives, detergents, dispersants, emulsifiers,
surfactants, defoamers, adhesion promoters, corrosion inhibitors,
viscosity improvers, lubricants, rheology modifiers, thickeners,
crosslinkers, paper treatment, water treatment, electronic
materials, paints, coatings, photography, ink materials, imaging
materials, superabsorbants, cosmetics, hair products,
preservatives, biocide materials or modifiers for asphalt, leather,
textiles, ceramics and wood.
[0172] Because the present polymerizaton is a "living"
polymerization, it can be started and stopped practically at will.
Furthermore, the polymer product retains the functional alkoxyamine
group allowing a continuation of the polymerization in a living
matter. Thus, in one embodiment of this invention, once the first
monomer is consumed in the initial polymerizing step a second
monomer can then be added to form a second block on the growing
polymer chain in a second polymerization step. Therefore it is
possible to carry out additional polymerizations with the same or
different monomer(s) to prepare multi-block copolymers.
[0173] Furthermore, since this is a radical polymerization, blocks
can be prepared in essentially any order. One is not necessarily
restricted to preparing block copolymers where the sequential
polymerizing steps must flow from the least stabilized polymer
intermediate to the most stabilized polymer intermediate, such as
is the case in ionic polymerization. Thus it is possible to prepare
a multi-block copolymer in which a polyacrylonitrile or a
poly(meth)acrylate block is prepared first, then a styrene or
butadiene block is attached thereto, and so on.
[0174] Furthermore, there is no linking group required for joining
the different blocks of the present block copolymer. One can simply
add successive monomers to form successive blocks.
[0175] A plurality of specifically designed polymers and copolymers
are accessible by the present invention, such as star and graft
(co)polymers as described, inter alia, by C. J. Hawker in Angew.
Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K.
Matyaszewski et al. in Macrmolecules 1996, Vol 29, No. 12, pages
4167-4171, graft (co)polymers as described by C. J. Hawker et al.
in Macromol. Chem. Phys. 198, 155-166(1997), random copolymers as
described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or
diblock and triblock copolymers as described by N. A. Listigovers
in Macromolecules 1996, 29, 8992-8993.
[0176] A further subject of the invention is the use of a compound
of formula Ia, Ib, Ic or Id for the controlled radical
(co)polymerization of ethylenically unsaturated monomers.
[0177] The compounds of formula Ia, Ib, Ic and Id are prepared
according to the following reaction scheme which is illustrative
for a compound of formula Ia: 20
[0178] The nitroxyl compounds are known and can be prepared by
known methods. Their preparation is for example described in GB
2335190, GB 2342649, and GB 2361 235.
[0179] Hal is halogen and preferably Br or Cl.
[0180] Multifunctional halogenated compounds can be prepared for
example by reacting a .alpha.-halogenated acid chloride or bromide
with a polyfunctional alcohol, polyfunctional aminoalcohol,
polyfunctional amine, polyfunctional mercaptane or polyfunctional
phenol. The preparation of multifunctional halogenated compounds
from polyfunctional alcohols and a .alpha.-halogenated acid
chloride is for example described in WO 00/43344.
[0181] If X is a direct bond and Z is --O--CH.sub.2--, then the the
multifunctional compounds may be prepared for example by reacting a
suitable derivative of a polycarboxylic acid, for example an acid
chloride with the corresponding alcohol according the equation:
21
[0182] The above educts are reacted to the compounds according to
formula Ia, Ib, Ic and Id in conventional solvents, such as for
examples cyclic ethers in accordance with the method described by
Matyjaszewski in U.S. Pat. No. 5,910,549.
[0183] A drawback of the process described in U.S. Pat. No.
5,910,549 is, that an excess of the nitroxyl compound has to be
used which remains in the end product. A separation and
purification is in most cases only possible by chromatography.
[0184] Since remaining nitroxyl radicals adversly affect the rate
of the polymerization reaction, it is highly desirable to remove
those radicals in an industrially feasible way. This problem has
been solved by the present invention by applying a reducing step at
the end of the reaction. The excess nitroxyl is reduced to the
corresponding hydroxylamine or amine which both are more basic than
the nitroxyl and thus can be washed out by an acid washing
step.
[0185] Surprisingly the alkoxyamine remains unaffected and the
yields remain high. The improvement is particularly useful in view
of an industrial production of such compounds.
[0186] A further subject of the invention is therefore a process
for the preparation of a compound of formula Ia, Ib, Ic or Id which
process comprises the steps of
[0187] a) reacting a compound of formula IIa, IIb, IIc or IId
22
[0188] with a compound of formula III 23
[0189] having a radically transferable group Hal, with a transition
metal complex in the absence of oxygen;
[0190] b) subjecting the reaction mixture to a reduction step;
[0191] c) washing the resulting mixture with an aqueous acid
solution and
[0192] d) isolating the product.
[0193] The definitions and preferences for the compounds of formula
Ia, Ib, Ic and Id have already been given and apply also for the
other subjects of the invention.
[0194] Complexing agents are known and for example described in
U.S. Pat. No. 5,910,549.
[0195] The reduction step can be performed by various methods, such
as for example by catalytic hydrogenation, with hydrazine or
dithionite. Preferred is a reduction with Na-dithionite.
[0196] The Na-dithionite is preferably used as an aqueous solution
or as a powder. The concentration of the aqueous solution may vary
from 0.1% to 40% by weight, preferred is 5% to 20%.
[0197] The acid used in the washing step is preferably a mineral
acid, such as HCl, but also organic sulfonic acids or complex acids
such HPF6 or HClO.sub.4 are suitable.
[0198] The reaction temperature is preferably from 0.degree. C. to
80.degree. C., more preferably from 10.degree. C. to 50.degree.
C.
[0199] The reaction time can vary in a wide range from 30 minutes
to 24 hours, depending on the educts. In most cases 2 hours to 16
hours are sufficient to complete the reaction.
[0200] The reaction is usually carried out under normal conditions.
However in some cases a slight pressure of up to 1 bar or a slight
evacuation to 200 mbar may be of advantage.
[0201] The coupling reaction per se is known and the concentrations
of the reactants may vary in a wide range as described in U.S. Pat.
No. 5,910,549.
[0202] The following examples illustrate the invention.
A) PREPARATION EXAMPLES
EXAMPLE A1
Compound 101
[0203] In a 100 ml three neck flask 7.75 g (36.1 mmol)
2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl (prepared
according to DE 199 09 767 A1, example 2), 5.19 g (36.1 mmol)
Cu(I)Br and 2.29 g (36.1 mmol) Cu(O)-powder are added. Oxygen is
removed from the reaction mixture by applying vacuum and flushed
with nitrogen. 50 ml dioxane and 6.0 g (18.1 mmol)
1,2-ethandiolbis(2-brompropionate) are added under stirring
homogenized (suspension of CuBr and Cu in dissolved edukts). With a
syringe 12.53 g (72.3 mmol) N,N,N',N",N"-Pentamethyldieth-
ylentriamine (PMDETA) are slowly added and the exothermal reaction
startedl. The temperature is kept at 20.degree. C. with an ice
bath. During the reaction the color of the suspension changes from
red to green. After 12 h stirring at 20.degree. C. After stirring
for 12 h at 20.degree. C. the reaction is stopped and the reaction
mixture is filtered over Tonsil Supreme 110FF (Sud Chemie). The
filtrate is concentrated under vacuum and 50 ml aetylacetate are
added: The solution is washed twice with 30 ml of a 10%
EDTA-solution (ethylandiamin tetraacetic acid disodium salt),
subsequently twice with 20 ml of a 10% freshly prepared sodium
dithionite solution and finally once with 20 ml of a 0.1 n HCl. The
organic phase is dried over Na.sub.2SO.sub.4, filtered off and the
filtrate is concentrated and dried at 60.degree. C. under vacuum.
6.7 g (62%) of compound 101 are obtained as a slightly yellow
resinous product.
[0204] Elemental Analysis:
[0205] Calculated C.sub.32H.sub.60N.sub.2O.sub.8: C 63.97%, H
10.07%, N 4.66%; Found: C 63.07%, H 10.05%, N 4.38%.
EXAMPLE A2
Compound 102
[0206] In analogy to example A1 4.28 g (20 mmol)
2,6-diethyl-2,3,6-trimeth- yl-4-hydroxy-piperidine-1-oxyl, 2.87 g
(20 mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40
mmol) PMDETA are reacted in 40 ml dioxane with 4.14 g (10 mmol)
1,4-cyclohexandiolbis(2-brompropionate). 6.4 g (97%) of compound
102 are obtained as slightly yellow solid resin.
[0207] Elemental Analysis:
[0208] Calculated C.sub.36H.sub.66N.sub.2O.sub.8: C 66.02%, H
10.16%, N 4.28%; Found: C 65.63%, H 10.04%, N 4.11%.
EXAMPLE A3
Compound 103
[0209] In analogy to example 1 4.28 g (20 mmol)
2,6-diethyl-2,3,6-trimethy- l-4-hydroxy-piperidine-1-oxyl, 2.87 g
(20 mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40
mmol) PMDETA are reacted in 40 ml dioxane with 3.86 g (10 mmol)
N,N'-Bis-(2-brompropionyl)-1,6 diaminohexane. 5.5 g (84%) of
compound 103 are obtained as white solid resin.
[0210] Elemental Analysis:
[0211] Calculated C.sub.36H.sub.70N.sub.4O.sub.6: C 66.02%, H
10.77%, N 8.55%; Found: C 65.33%, H 10.70%, N 8.12%.
EXAMPLE A4
Compound 104
[0212] In analogy to example 1 4.25 g (20 mmol)
2,6-diethyl-2,3,6-trimethy- l-4-oxo-piperidine-1-oxyl, 2.87 g (20
mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol)
PMDETA are reacted in 40 ml dioxane with 3.86 g (10 mmol)
N,N'-Bis-(2-brompropionyl)-1,6-diaminohexane. 5.6 g (85%) of
compound 104 are obtained as pale white solid resin.
[0213] Elemental Analysis:
[0214] Calculated C.sub.36H.sub.70N.sub.4O.sub.6: C 66.43%, H
10.22%, N 8.61%; Found: C 66.01%, H 9.90%, N 8.22%.
EXAMPLE A5
Compound 105
[0215] In analogy to example 1 4.28 g (20 mmol)
2,6-diethyl-2,3,6-trimethy- lhydroxy-piperidine-1-oxyl, 2.87 g (20
mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol)
PMDETA are reacted in 40 ml dioxane with 6.24 g (10 mmol)
poly(ethylene glycole-400)-bis(2-brompropionate). 5.7 g (67%) of
compound 105 are obtained as pale white solid resin.
EXAMPLE A6
Compound 106
[0216] In analogy to example 1 4.28 g (20 mmol)
2,6-diethyl-2,3,6-trimethy- lhydroxy-piperidine-1-oxyl, 2.87 g (20
mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol)
PMDETA are reacted in 40 ml dioxahe with 6.249 (10 mmol)
poly(tetrahydrofuran-250)-bis(2-brompropionate). 6.1 g (77%) of
compound 106 are obtained as pale white solid resin.
EXAMPLE A7
Compound 107
[0217] In analogy to example A1 3.21 g (15 mmol)
2,6-Diethyl-2,3,6-trimeth- yl-4-hydroxy-piperidine-1-oxyl, 2.15 g
(15 mmol) Cu(I)Br, 191 mg (3 mmol) Cu(O)-powder and 2.60 g (0.15
mmol) PMDETA are reacted in 15 ml ethylacetate with 2.69 g (5 mmol)
tris-(2'-brompropionyl)-1,1,1-trimethyl- olpropane (prepared
according to WO 00/43344) for 20 h at R.T. 2.42 g (51%) of compound
108 are obtained as a white powder.
[0218] Elemental Analysis:
[0219] Calculated C.sub.51H.sub.95N.sub.3O.sub.12: C 65.01%, H
10.16%, N 4.46%; Found: C 63.69%, H 9.86%, N 4.40%.
[0220] Maldi-TOF-MS: M.sup.+: 942 (as calculated).
EXAMPLE A8
Compound 108
[0221] In analogy to example 1 3.21 g (15 mmol)
2,6-diethyl-2,3,6-trimethy- l-4-hydroxy-piperidine-1-oxyl, 2.15 g
(15 mmol) Cu(I)Br, 191 mg (3 mmol) Cu(O)-powder and 2.60 g (15
mmol) PMDETA in 15 ml ethylacetate are reacted with 2.86 g (5 mmol)
Tris-(2'-brompropionyl)phloroglucine (prepared in accordance with
WO 00/43344) for 18 h at R.T. 4.05 g (83%) of compound 109 are
obtained as a white orange powder.
EXAMPLE A9
Compound 109
[0222] In analogie to example 1 4.28 g (20 mmol)
2,6-Diethyl-2,3,6-trimeth- ylhydroxy-piperidine-1-oxyl, 2.87 g (20
mmol) Cu(I)Br, 318 mg (5 mmol) Cu(O)-powder and 3.46 g (20 mmol)
PMDETA in 15 ml ethylacetat are reacted with 3.38 g (5 mmol)
tetrakies-(2'-brompropionyl)pentaerythrite (prepared in accordance
with WO 00/43344) umgesetzt (20 h, R.T.). 4.75 g (78%) of compound
110 are obtained as a white powder.
[0223] Elemental Analysis:
[0224] Calculated C.sub.65H.sub.120N.sub.4O.sub.16: C 64.38%, H
9.97%, N 4.62%; Found: C 63.75%, H 9.76%, N 4.49%.
[0225] Maldi-TOF-MS: M.sup.+: 1213 (as calculated).
EXAMPLE A10
Compound 110
[0226] In analogy to example 1 2.57 g (12 mmol)
2,6-diethyl-2,3,6-trimethy- l-4-hydroxy-piperidine-1-oxyl, 1.18 g
(12 mmol) Cu(I)Cl, 152 mg (2.4 mmol) Cu(O)-powder and 2.08 g (12
mmol) PMDETA in 15 ml ethylacetate are reacted with 1.45 g (2 mmol)
Hexakis-(2'-chlorpropionyl)sorbitol (prepared in accordance with WO
00/43344) for 15 h at R.T. 3.0 g (84%) of compound 111 are obtained
as an off white powder.
[0227] Elemental Analysis:
[0228] Calculated C.sub.96H.sub.176N.sub.6O.sub.24: C 64.11%, H
9.86%, N 4.67%; Found: C 63.20%, H 9.57%, N 4.25%.
EXAMPLE A111
Compound 111
[0229] In analogy to example A1 3.06 g (12 mmol)
1-t-butyl-3,3-diethyl-5,5- -dimethylpiperazin-2-on-4-oxyl (prepared
in accordance with DE 19949352 A1, example B38), 1.72 g (12 mmol)
Cu(I)Br, 0.76 g (12 mmol) Cu(O)-powder and 4.24 g (24 mmol) PMDETA
are reacted in 25 ml toluene with 1.99 g (6 mmol)
1,2-ethandiolbis(2-brompropionate). 1.96 g (48%) of compound 111
are obtained as a colorless resinous product.
[0230] Elemental Analysis:
[0231] Calculated C.sub.36H.sub.66N.sub.4O.sub.8; C 63.31%, H
9.74%, N 8.20%; Found: C 63.09%, H 9.58%, N 7.77%.
EXAMPLE A112
Compound 112
[0232] In analogy to example A1 5.0 g (25 mmol) 3,3-diethyl-5,5
dimethylmorpholin-2-on-4-oxyl (prepared in accordance with DE
19949352 A1, example B8), 3.70 g (25 mmol) Cu(I)Br, 1.60 g (25
mmol) Cu(O)-powder and 8.84 g (50 mmol) PMDETA are reacted in 50 ml
toluene with 4.15 g (12.5 mmol) 1,2-ethandiolbis(2-brompropionate).
6.57 g (92%) of compound 112 are obtained as a colorless resinous
product.
[0233] Elemental Analysis:
[0234] Calculated C.sub.28H.sub.48N.sub.2O.sub.10; C 58.72%, H
8.45%, N 4.89%; Found: C 58.98%, H 8.46%, N 4.78%.
[0235] The compounds are summarized in Table 1.
1TABLE 1 Compounds prepared Compound no. Structure 101 24 102 25
103 26 104 27 105 28 106 29 107 30 108 31 109 32 110 33 111 34 112
35
B POLYMERIZATION EXAMPLES
POLYMERIZATION EXAMPLES IN STYRENE
[0236] General Remarks:
[0237] Styrene and the other monomers are distilled over a Vigreux
column under vacuum, shortly before being used.
[0238] To remove oxygen all polymerization reaction mixtures are
flushed before polymerization with argon and evacuated under vaccum
applying a freeze-thaw cycle. The reaction mixtures are then
polymerized under argon atmosphere.
[0239] At the start of the polymerization reaction, all starting
materials are homogeneously dissolved.
[0240] Conversion is determined by removing unreacted monomers from
the polymer in a vacuum oven at 70.degree. C. and 0.01 torr for at
least 24 hours, weighing the remaining polymer and subtracting the
weight of the initiator.
[0241] Characterization of the polymers is carried out by GPC (Gel
Permeation Chromatography).
[0242] GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS.
Tetrahydrofuran (THF) is used as a solvent and is pumped at 1
ml/min. Two chromatography columns are put in series: type PIgel 5
.mu.m mixed-C of POLYMER INSTRUMENTS, Shropshire, UK. Measurements
are performed at 40.degree. C. The columns are calibrated with low
polydispersity polystyrenes having Mn from 200 to 2000000 Dalton.
Detection is carried out using a R.sub.1-Detector or UV-Detector at
30.degree. C.
EXAMPLE B1
Polymerization of Styrene with 0.5 mol % of Compound 102 (Table 1)
at 130.degree. C.
[0243] In a 100 ml schlenck flask, equipped with magnetic stirrer,
0.972 g (1.48 mmol) of compound 102 and 30.9 g (297 mmol) of
styrene are mixed and degassed. The clear solution obtained is
stirred under argon at 130.degree. C. and polymerization is carried
out during 6 h. The reaction mixture is then cooled to RT. The
remaining monomer is removed by evaporation under high vacuum at
70.degree. C. 21.8 g (70.6%) of the initial monomer have reacted. A
slightly yellow solid is obtained.
[0244] Mn=13780, Mw=17360, PD=1.26
EXAMPLE B2
Polymerization of Styrene with 0.5 mol % of Compound 103 (Table 1)
at 130.degree. C.
[0245] In a 100 ml schlenck flask, equipped with magnetic stirrer,
0.974 g (1.49 mmol) of compound 103 and 31.0 g (297 mmol) of
styrene are mixed and degassed. The clear solution obtained is
stirred under argon at 130.degree. C. and polymerization is carried
out during 6 h. The reaction mixture is then cooled to RT. The
remaining monomer is removed by evaporation under high vacuum at
70.degree. C. 22.7 g (73.4%) of the initial monomer have reacted. A
white solid is obtained.
[0246] Mn=1520, Mw=23980, PD=1.58
EXAMPLE B3
Polymerization of Styrene with 0.5 mol % of Compound 104 (Table 1)
at 130.degree. C.
[0247] In a 100 ml schlenck flask, equipped with magnetic stirrer,
0.525 g (0.81 mmol) of compound 104 and 16.8 g (161 mmol) of
styrene are mixed and degassed. The clear solution obtained is
stirred under argon at 130.degree. C. and polymerization is carried
out during 6 h. The reaction mixture is then cooled to RT. The
remaining monomer is removed by evaporation under high vacuum at
70.degree. C. 13.1 g (78.1%) of the initial monomer have reacted. A
white solid is obtained.
[0248] Mn=17420, Mw=25550, PD=1.47
POLYMERIZATION EXAMPLES IN ACRYLATES
EXAMPLE B4
Polymerization of n-BuA with Compound 102 (Table 1)
[0249] A round-bottom three necked flask, equipped with
thermometer, condenser and magnetic stirrer is charged with 0.383 g
(0.59 mmol) of compound 102 and 10 g (78 mmol) of n-butylacrylate
and degassed. The clear solution is then heated to 145.degree. C.
under argon. The mixture is stirred for 5 hours at 145.degree. C.
and then cooled to 60.degree. C. and the remaining monomer is
evaporated under high vacuum. 7.9 g (79%) of the monomer are
reacted and a yellow turbid viscous liquid is obtained.
[0250] GPC: Mn=11000, Mw=15070, Polydispersity index=1.37
EXAMPLE B5
Polymerization of n-BuA with Compound 103 (Table 1)
[0251] A round-bottom three necked flask, equipped with
thermometer, condenser and magnetic stirrer is charged with 0.383 g
(0.59 mmol) of compound 103 and 10 g (78 mmol) of n-butylacrylate
and degassed. The clear solution is then heated to 145.degree. C.
under argon. The mixture is stirred for 5 hours at 145.degree. C.
and then cooled to 60.degree. C. and the remaining monomer is
evaporated under high vacuum. 7.9 g (79%) of the monomer are
reacted and a yellow viscous liquid is obtained.
[0252] GPC: Mn=11650, Mw=17475, Polydispersity index=1.5
EXAMPLE B6
Polymerization of n-BuA with Compound 111
[0253] A round-bottom three necked flask, equipped with
thermometer, condenser and magnetic stirrer is charged with 0.403 g
(0.59 mmol) of compound 111 and 10 g (78 mmol) of n-buthylacrylate
and degassed. The clear solution is then heated to 145.degree. C.
under argon. The mixture is stirred for 5 hours at 145.degree. C.
and then cooled to 60.degree. C. and the remaining monomer is
evaporated under high vacuum. 7.2 g (72%) of the monomer are
reacted and a yellow viscous liquid is obtained.
[0254] GPC: Mn=9710, Mw=12050, polydispersity index PD=1.24
EXAMPLE B7
Polymerization of n-BuA with Compound 112
[0255] A round-bottom three necked flask, equipped with
thermometer, condenser and magnetic stirrer is charged with 0.338 g
(0.59 mmol) of compound 112 and 10 g (78 mmol) of n-buthylacrylate
and degassed. The clear solution is then heated to 145.degree. C.
under argon. The mixture is stirred for 5 hours at 145.degree. C.
and then cooled to 60.degree. C. and the remaining monomer is
evaporated under high vacuum. 7.8 g (78%) of the monomer are
reacted and a yellow viscous liquid is obtained.
[0256] GPC: Mn=9890, Mw=12960, polydispersity index PD=1.31
* * * * *